The kinetics of solute segregation to partial dislocations in a Cu–3.4 At.% Sb alloy was studied by using a phenomenological approach with differential scanning calorimetry and isothermal calorimetry. The material, severely deformed by repeated bending, presented an excess of dissociated edge dislocations with a dislocation density amounting to about 8.5·1014 m–2, calculated using a prior model of the authors, together with calorimetric recrystallization trace analysis. The kinetics was found to be ruled by two overlapping mechanisms: diffusion of solute atoms mostly through dislocation pipes in the initial and middle stages of the reaction process, acting together with bulk solute diffusion in these stages and later. Bulk solute diffusion increases as the reaction proceeds, as shown by the increasing values of apparent activation energy in the reaction. The exponent of the Mehl-Johnson-Avrami equation used in the phenomenological description was successfully fitted to a time—temperature-dependent function, increasing in agreement with the apparent activation energy behaviour, as may be expected.
A model is proposed to describe the kinetics of solute segregation to partial dislocations in solid solutions of cold-rolled
alloys. The case when half edge and half screw dislocations are present is considered. The model gives account of the kinetic
behaviour observed in a deformed Cu-19 at% Al alloy where two unknown processes could be assessed during calorimetric isothermal
experiments. The faster process corresponds to segregation to screw dissociated dislocations while the slower one corresponds
to segregation to edge dissociated dislocations. Experimental activation energies, larger for edge dislocations, are close
to that for pipe diffusion along the partials corrected by pinner binding energy terms. It is also predicted that segregation
occurs faster as the dislocation density is increased. A quantitative comparison of experimental results with model predictions
A general model is discussed for assessing the energy release due to the pinning of solute atoms to partial dislocations. The present approach discloses the influence of dislocation character distributions on the magnitude of this energy. In order to test its validity in αCu-Al alloys, differential scanning calorimetry (DSC) evaluations associated with the different peaks involved during linear heating were performed employing both cold worked and quenched materials. Dislocation densities were calculated from recrystallization traces. On the basis of this model it was concluded that the observed energy difference between the deformed and the quenched materials during the exothermic peak designated as Stage 2 corresponds to the pinning process. It was also concluded that nearly equal number of edge and screw dislocations are present in the dislocation configuration of deformed alloys. Nevertheless, it is proposed that dislocation-induced order might also occur as a consequence of enhanced solute concentration around the partials.
A model describing the roles of bound and unbound vacancies is proposed in order to predict defect decay and short-range-order
kinetics of quenched binary alloys during linear heating experiments. This is an alternative treatment of a previous approach.
The model has been applied to the differential scanning calorimetry (DSC) curves of Cu-5 at.% Zn quenched from different temperatures.
An expression to calculate the activation energy for migration of solute-vacancy complexes was also developed which make use
of DSC trace data. A value of 89.120.32 kJ mol-1 was obtained for the above alloy. The relative contribution of bound and unbound vacancies to partition of effective activation
energy corresponding to the ordering process as influenced by quenching temperature was also assessed.
Using differential scanning calorimetry (DSC) the precipitation processes of supersaturated solid solutions of three Cu-Co-Si
alloys containing the same atomic cobalt content were investigated. Thermoanalytical and previous studies, reveal that the
decomposition begins with cobalt clustering which initiates the precipitation of the Co2Si stoichiometric particles, which in turn dissolves after further heating. Volume fractions are unequivocally determined
by the amount of cobalt present in these alloys. It is infered that surplus silicon atoms retained in the solution increase
the reaction rate and dispersity of precipitate structure. Kinetic parameters were obtained by a convolution method based
in the Mehl-Johnson-Avrami (MJA) formalism. The lower activation energy associated with cobalt clustering is attributed to
the contribution of quenched-in vacancies. Superimposed to the MJA formalism and adaptative spherical diffusion model was
used for Co2Si precipitation with particle size as a disposable parameter. This model further confirmed that as silicon content increases
particle dispersity becomes more pronounced. Such results are also infered from a three dimensional diffusion dissolution
model previously developed which adjusts quite well to such process in the present cases. Age hardening experiments are in
line with all previous results obtained.
Beryllium precipitation from the Cu-rich matrix in a Cu–2 mass% Be–0.2 mass% Mg alloy homogenized and quenched from 1073 K was studied by differential scanning calorimetry (DSC). The DSC traces showed two main exothermic effects, A and B, each comprising two subeffects: A1 and A2 , and B1 and B2 respectively. Effects A1 and A2 correspond to the precipitation of GP zones and subsequent overlapping and independent precipitation of the
phase. Only at very low heating rates can
be inherited from GP zones. Effects B1 and B2 correspond to heat evolved during transitions to the states with
and phases, respectively. Heat effect A can be quantitatively described in terms of solid solubilities before and after precipitation, and of the precipitation heats of the phases involved. The heat content of the combined GP zone/
phase precipitation effect was proportional to the number of beryllium atoms precipitated, yielding an average value of 21 kJ mol–1 beryllium for beryllium precipitation. It was shown that the
phase arises from the combined transition from states with GP zones and
phases, whereas arises from the transition of states with
phases. The apparent activation energies associated with GP zones and
and phases are 1.16±0.08, 1.18±0.07, 1.37±0.08 and 1.74±0.09 eV, respectively. These values are discussed in terms of the mobility of dissolved atoms related to the concentrations of excess vacancies and solute-vacancy complexes, and the direction of plate-like precipitate growth (either normal or perpendicular to the plate). It is inferred that the main roles of magnesium are to decrease the amount and rate of GP formation, to enhance the volume fraction of
and to suppress the discontinuous precipitation of
A modified first order kinetic law, which describes the roles of bound and unbound vacancies, is proposed in order to predict
defect decay and short-range-order kinetics of quenched binary alloys during linear heating experiments. The model has been
applied to differential scanning calorimetry (DSC) curves of Cu–5 at%Zn quenched from different temperatures. Activation energy
for migration of solute-vacancy complexes was also assessed from the kinetics of short-range-order using DSC traces. A value
of 89.50.32 kJ mol–1 was obtained. The relative contribution of bound and unbound vacancies to the ordering process as influenced by quenching
temperature was determined. In conjunction, a parametric study of the initial total defect concentration and effective energy
for defect migration was performed in order to envisage their influence on the calculated DSC profiles.
A modified first-order kinetic law which takes into account defect decay during an ordering process was employed to predict the short-range-order kinetics of a quenched and a quenched-deformed Cu—5 at.% Zn alloy, in conjunction with experiments performed by isothermal calorimetry. The effective activation energy of point defect migration and its temperature dependence strongly suggest the contribution of bound vacancies to the ordering process. An estimate of 91.2 kJ mol–1 was made for the activation energy of solute—vacancy migration by applying an effective rate constant, a value in very good agreement with that obtained from previous non-isothermal experiments. The isothermal curves were utilized to determine the ordering energy: w=–2.90 kJ mol–1. In conjunction, a parametric study of the defect sink density was performed in order to assess its influence on the calculated isothermal curve profiles.
By means of differential scanning calorimetry (DSC) the precipitation process from a supersaturated solid solution of Cu−0.65
at% Co−0.33 at% Si (Cu−1 at% Co2Si) was investigated. On the basis of enthalpimetric calculations it was found that the decomposition
begins with cobalt precipitation. Clustering of atoms of cobalt initiates the precipitation of silicon, and particles of the
stoichiometric Co2Si composition are finally formed. Kinetic parameters were obtained by a convolution method based on the
Mehl–Johnson–Avramiformalism. Their values are all in agreement with the experimentally observed behavior displayed by DSC
traces. Decay kinetics of cobalt and silicon matrix during simulated isothermal calculations using DSC data reveals good agreement
with similar computed results reported in literature. Precipitate dissolution obeys quite well to a three-dimensional diffusion
kinetic law previously developed.